WO2006126521A1 - Structure de film de revetement resistant aux taches - Google Patents

Structure de film de revetement resistant aux taches Download PDF

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Publication number
WO2006126521A1
WO2006126521A1 PCT/JP2006/310217 JP2006310217W WO2006126521A1 WO 2006126521 A1 WO2006126521 A1 WO 2006126521A1 JP 2006310217 W JP2006310217 W JP 2006310217W WO 2006126521 A1 WO2006126521 A1 WO 2006126521A1
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WIPO (PCT)
Prior art keywords
boiling point
coating film
organic solvent
hydrophobic polymer
antifouling coating
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PCT/JP2006/310217
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English (en)
Japanese (ja)
Inventor
Tarou Kuroda
Shigeharu Taira
Satoki Nakada
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Daikin Industries, Ltd.
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Publication of WO2006126521A1 publication Critical patent/WO2006126521A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/16—Antifouling paints; Underwater paints
    • C09D5/1606—Antifouling paints; Underwater paints characterised by the anti-fouling agent
    • C09D5/1612—Non-macromolecular compounds
    • C09D5/1618—Non-macromolecular compounds inorganic
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/66—Additives characterised by particle size
    • C09D7/67—Particle size smaller than 100 nm
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica

Definitions

  • the present invention relates to a structure of an antifouling coating film that is excellent in antifouling properties and that can use a general-purpose paint resin.
  • the current situation in antifouling technology is that the surface is highly hydrophobic (water / oil repellency), the surface is highly hydrophilic, the photocatalyst is added, and the surface of the coating is micronized. It is known to use a phase-separated structure to prevent both hydrophilic and hydrophobic dirt from adhering.
  • JP-A-2003-211569 discloses that each of 0.04 and later: L Ocm 2 hydrophilic coating region and hydrophobic coating region are alternately arranged to prevent rain stains.
  • the hydrophilic / hydrophobic structure with such a large area has sufficient anti-adhesion ability in the field of anti-adhesion in general-purpose articles such as outdoor articles exposed to a wide variety of air-borne contaminants. Can't be achieved! /
  • the present invention forms a uniform antifouling coating film surface regardless of the type of coating polymer, although the amount of hydrophilic particles is low as a whole. It is to provide the structure of the coating film to be obtained.
  • the present inventors have repeated intensive experiments and considerations, and overturned the conventional common knowledge that a large amount of hydrophilic particles are necessary to exhibit antifouling properties. As a result of obtaining the knowledge that the antifouling property is improved in a low content range and further studying the application range based on such knowledge, the inventors have completed the invention according to the structure of the present invention.
  • the present invention relates to a coating film structure in which 10 to 50 parts by mass of hydrophilic particles (A) are dispersed in 100 parts by mass of a hydrophobic polymer (B), and the hydrophilic particles (A)
  • the structure of the antifouling coating film is characterized in that the number average particle diameter of the coating film is 50 nm or less and the surface on the free surface side of the coating film has a surface roughness a of 50 nm or less at a reference length of 500 nm About.
  • the surface roughness a is 50 nm or less, and it is more preferable if the surface roughness a is 25 nm or less.
  • the coating film structure may have a surface layer (b1) substantially consisting of the hydrophobic polymer (B) in the outermost layer on the free surface side.
  • hydrophilic particles (A) include silica fine particles, titanium oxide fine particles, apatite fine particles, apatite and Z or metal fine particles having photocatalytic activity.
  • the hydrophobic polymer (B) may be a crosslinkable polymer or a non-fluorinated hydrophobic polymer.
  • the present invention also relates to an air conditioner, an electrical appliance, and a member for an air passage constituted by a member having an antifouling coating film having the structure of the present invention on the substrate surface.
  • the antifouling coating film having the structure of the present invention can also be formed on a base material made of rosin.
  • FIG. 1 is a schematic cross-sectional schematic view of one embodiment of the antifouling coating film of the present invention.
  • FIG. 2 is a transmission electron micrograph (TEM: 160,000 times) of the cross section of the coating film formed in Example 1.
  • FIG. 3 Transmission electron micrograph of the cross section of the coating film formed in Example 2 (TEM: 160, 000 Times).
  • FIG. 4 is a transmission electron micrograph (TEM: 160,000 times) of a cross section of a coating film formed in Example 3.
  • FIG. 5 is a transmission electron micrograph (TEM: 160,000 times) of the cross section of the coating film formed in Comparative Example 1.
  • FIG. 6 is a schematic view of an antifouling test apparatus used in the accelerated antifouling test employed in Examples 1 to 3 and Comparative Example 1.
  • the number average particle diameter of the hydrophilic particles (A) is 50 nm or less
  • the surface on the free surface side of the coating film has a surface roughness a of 50 nm or less over a length of at least 1 m.
  • FIG. 1 is a schematic cross-sectional schematic view of one embodiment of the antifouling coating film of the present invention.
  • A is a hydrophilic particle having a number average particle diameter of 50 nm or less
  • B is a hydrophobic polymer.
  • the content of the hydrophilic particles (A) is 10 to 50 parts by mass with respect to 100 parts by mass of the hydrophobic polymer (B), and is dispersed in the hydrophobic polymer (B).
  • the content of the hydrophilic particles (A) is preferably 10 parts by mass or more, more preferably 15 parts by mass or more with respect to 100 parts by mass of the hydrophobic polymer (B).
  • the absolute amount of the nearby hydrophilic particles (A) decreases, and the intended antifouling effect cannot be obtained.
  • Hydrophilic particles (A) can be used only on the antifouling surface even if they exceed 50 parts by mass.
  • the coating properties, the mechanical strength of the coating, the price, the stability of the materials, and the storage stability are important.
  • the force is preferably 45 parts by mass or less, more preferably 30 parts by mass or less.
  • the number average particle diameter of the hydrophilic particles (A) is 50 nm or less, which is preferable in terms of being effective in preventing adhesion of bacteria and organisms and ensuring transparency of the coating film. More preferably, it is 39 nm or less, particularly 15 nm or less. The lower limit is 5 nm or more, and it is widely adhered to dirt. Preferable in terms of preventing. Specifically, it is selected from the range of 50 nm or less depending on the environment of use and the attached substance. The number average particle diameter can be determined by reading an electron micrograph.
  • hydrophilic particles (A) and the hydrophobic polymer (B) will be described in detail in the description of the composition used for forming the antifouling coating film of the present invention.
  • a characteristic of the antifouling coating film of the present invention is that the surface on the free surface side of the coating film does not simply have the hydrophilic particles (A) present in the vicinity of the surface, and the surface roughness a of at least 1 is 50 nm or less. It is important that the surface has a length of ⁇ m (element (c)).
  • the surface roughness a is the lowest in the outermost surface layer (bl) made of the hydrophobic polymer (B).
  • the point (valley bottom) force is the highest! It is the height to the point (mountain peak).
  • the surface roughness a is preferably 50 nm or less, preferably 40 nm or less, more preferably 30 nm or less, and particularly preferably 25 nm or less. If the surface roughness a is too large from the experimental results, dirt is attached. It seems that as the surface becomes larger, it becomes easier to attract dirt. It is presumed that it is preferable that the surface is as smooth as possible because the surface to which dirt adheres becomes smaller and the dirt also becomes difficult to pull.
  • the lower limit of the surface roughness a is 5 nm, further 3 nm, especially lnm.
  • the coating film structure of the present invention has a reference length of 500 nm, and further a region having a surface roughness a of 50 nm or less at a reference length of 1 ⁇ m.
  • a sufficient antifouling effect cannot be obtained in that the dirt that floats in the atmosphere is easily attracted.
  • the surface roughness a can also be read as an electron microscopic photographic power.
  • the coating film exhibits excellent antifouling properties when it has a structure satisfying all the elements (a) to (c).
  • a paint that contains hydrophilic particles such as a hard coat agent that is usually commercially available has a small amount of hydrophilic particles on the surface of the coating film. Therefore, it is considered that the antifouling effect is high.
  • the degree of dispersion of the hydrophilic particles in the coating film satisfies, for example, the relationship of the following inequality (1).
  • cl is ⁇ ⁇ ⁇ !
  • This formula (2) indicates that hydrophilic particles (A1) with a density of 1Z3 times or more of hydrophilic particles (A2) with deep coating surface force exist in the vicinity of the coating surface.
  • hydrophilic particles (A1) existing near the surface may act on the flatness of the surface to improve the antifouling property.
  • the particle density can be determined by reading the number of particles on a line having a specific length at a predetermined depth from an electron micrograph of a cross section of the coating film.
  • the coating film may have an outermost surface layer (bl) substantially consisting of the hydrophobic polymer (B) in the outermost layer on the free surface side.
  • the average thickness of the outermost surface layer (bl) is preferably 50 nm or less.
  • the thinner the outermost surface layer (bl), the preferred average thickness is 45 nm or less, particularly 30 nm or less. This is preferable in terms of obtaining the effect of hydrophilic particles.
  • the surface roughness a is 50 nm or less.
  • the method for forming the structure of the antifouling coating film of the present invention includes hydrophilic particles (A), a hydrophobic polymer (B) for paint, an organic solvent (C) for the hydrophobic polymer for paint, and the like.
  • the other organic solvent (D) is a high-boiling organic solvent having a boiling point of 5 ° C. or more higher than the boiling point of the organic solvent (C) for the hydrophobic polymer for paints,
  • the antifouling paint composition (hereinafter referred to as “specific antifouling paint composition”) in which the ratio of the hydrophilic particles (A) Z hydrophobic polymer (B) is 1Z99 to 50Z50 (mass% ratio). There is also a method of applying the other).
  • boiling point is a boiling point under 1 atm, and when the boiling point is expressed in a temperature range, the intermediate value is ⁇ ⁇ .
  • the other organic solvent (D) functions as a dispersion medium for the hydrophilic particles ( ⁇ ), and the desired force is more hydrophilic than the hydrophobic polymer ( ⁇ ) for paint.
  • Affinity with ( ⁇ ) It can be expensive.
  • the organic solvent (C) and the organic solvent (D) may be a polar organic solvent, and V, one of them is a polar organic solvent and the other is nonpolar.
  • An organic solvent may be used, but as a particularly preferable combination, the organic solvent (C) for the hydrophobic polymer (B) for coating is a nonpolar organic solvent (C1), and the other organic solvent (D). Is a polar organic solvent (D1) for dispersing the hydrophilic particles (A).
  • One of the features of this embodiment is that a high-boiling polar organic solvent (D1) (for example, a boiling point of 115 ° C or higher and a relatively high boiling point solvent) and its high-boiling polar organic solvent (D1)
  • a nonpolar organic solvent (C1) having a boiling point of 5 ° C or higher is used in combination.
  • hydrophilic particles are used as a dispersion medium in the hydrophobic polymer solution for coating in which the hydrophobic polymer for coating is dissolved in the nonpolar organic solvent. It is thought that it is uniformly dispersed at a low concentration with a high boiling polar organic solvent. When the hydrophilic particles exceed a certain concentration, aggregation of the hydrophilic particles starts and the uniform dispersion state is broken. Therefore, it is necessary that the hydrophilic particles have a range where such aggregation phenomenon does not occur.
  • the problem is that the coating film is formed while maintaining a strong uniform dispersion state.
  • the boiling point of the polar organic solvent in which the hydrophilic particles are uniformly dispersed is higher than that of the nonpolar organic solvent. Therefore, during the formation and drying of the coating film, the non-polar organic solvent first evaporates, and the concentration of the hydrophobic polymer for coating in the coating film rises and starts to form the coating film matrix.
  • the polar organic solvent not only has a high boiling point, but also has an affinity for hydrophilic particles, so that the volatilization rate is slow. As a result, it is considered that the coating film is formed while maintaining the uniformly dispersed state of the hydrophilic particles.
  • the organic solvent (C) for coating is used to form a matrix layer by uniformly dissolving and dispersing the hydrophobic polymer (B) for coating, and has a boiling point of other organic solvents (D ) 5 ° C lower than
  • the specific organic solvent (C) differs depending on the boiling point of the other organic solvent (D) used, and other organic solvents (D) with a high boiling point are used.
  • the boiling point of the organic solvent (C) need not be 115 ° C or lower.
  • the organic solvent for paint (C) may be a polar organic solvent (C2) as long as it can dissolve the hydrophobic polymer for paint (B) to form a coating film.
  • the nonpolar organic solvent (C1) is preferred.
  • nonpolar organic solvent (C1) examples include, for example, aromatic hydrocarbon solvents having a boiling point of 80 to 150 ° C and aliphatic hydrocarbon solvents having a boiling point of 50 to 130 ° C. it can
  • Examples of the aromatic hydrocarbon solvent having a boiling point of 80 to 150 ° C include benzene (boiling point 80. 1 ° C), toluene (boiling point 110 ° C), xylene (boiling point 140 ° C), ethylbenzene (boiling point 136). ° C) and styrene (boiling point 145 ° C).
  • Examples of the aliphatic hydrocarbon solvent having a boiling point of 50 to 130 ° C include n-hexane (boiling point 65 to 69 ° C), heptane (boiling point 93 to 99 ° C), octane (boiling point 110 to 116).
  • isooctane (boiling point 102-113 ° C), isohexane (boiling point 57-61 ° C), isobutane (boiling point 80-91 ° C), cyclohexane (boiling point 81 ° C), n-heptane ( Examples include boiling point 98 ° C., trimethylpentane (boiling point 99 ° C.), methylcyclohexane (boiling point 10 etc.). These may be used by mixing the same or different solvents.
  • the polar organic solvent for paint (C2) is selected from a high-boiling polar organic solvent (D1) and a low-boiling polar organic solvent (D2) described later.
  • the other organic solvent (D) is used to uniformly and stably disperse the hydrophilic particles in the coating composition, and to maintain the uniform dispersion during the formation of the coating film.
  • polar solvents are preferred, and high boiling point polar organic solvents (D1) having a boiling point of 115 ° C. or higher are particularly preferred.
  • non-polar organic solvents can be used as long as they have equivalent functions.
  • Non-polar organic solvents that can be used as such other organic solvents (D) include non-polar organic solvents (C1) for hydrophobic polymers (B) for paints from among the above-mentioned non-polar organic solvents (C1). Examples having a boiling point higher by 5 ° C or more can be exemplified.
  • preferred high boiling polar organic solvent (D1) is a high boiling polarity polar solvent having a boiling point of 115 ° C or higher, more preferably 150 ° C or higher, 250 ° C or lower, and further 210 ° C or lower.
  • the organic solvent may be selected in consideration of the nonpolar organic solvent (C1) to be combined. Boiling point If the temperature is lower than 115 ° C, it may be difficult to form a coating film while maintaining uniform dispersibility. On the other hand, if it is too high, it tends to take too much time to form a coating film or to inhibit curing.
  • Specific examples include ether solvents having a boiling point of 120 to 250 ° C, high-boiling alcohol solvents having a boiling point of 115 to 250 ° C, ester solvents having a boiling point of 115 to 250 ° C, and boiling points of 115 to 220 ° C.
  • Examples include C ketone solvents and ester ether solvents having a boiling point of 135 to 225 ° C.
  • ether solvents having a boiling point of 120 to 250 ° C include ethylene glycol monoethyl ether (boiling point 135 ° C), ethylene glycol monobutyl ether (boiling point 170 ° C), propylene glycol monomethyl ether (PGME, boiling point 120 ° C), diethylene glycol monoethyl ether (boiling point 200 ° C), diethylene glycol monobutyl ether (boiling point 225 ° C), diethylene glycol jetyl ether (boiling point 189 ° C), jetyl ether (boiling point 121.4 ° C), monobutyl ether (Boiling point 171.2 ° C), mono n-hexyl ether (boiling point 208.3 ° C), monophenyl ether (boiling point 244.7 ° C), mono-2-ethylbutyl ether (boiling point 196.8 ° C
  • Examples of high boiling alcohol solvents having a boiling point of 115 to 250 ° C include n-butanol (boiling point 117 ° C), methoxybutanol (boiling point 160 ° C), diaceto alcohol (boiling point 168 ° C), cyclohexane Hexanol (boiling point 161 ° C), ethylene glycol (boiling point 197 ° C), propylene glycol (boiling point 188 ° C), 1,4 butanediol (boiling point 235 ° C), n-amyl alcohol (boiling point 138 ° C), isoamyl alcohol (boiling point 130.5 ° C), 3-methoxybutyl alcohol (boiling point 157-162 ° C), n-hexyl alcohol (boiling point 157.2 ° C), 2-methylpentanol ( Boiling point 147.5 ° C), sec He
  • ester solvents having a boiling point of 115 to 250 ° C examples include isoamyl formate (boiling point 124.
  • Examples of ketone solvents having a boiling point of 115 to 220 ° C include methyl isobutyl ketone (boiling point 116 ° C), butyl n-butyl ketone (boiling point 127.2 ° C), 2.4 pentanedione (boiling point 140. 5 ° C), ethylbutylketone (boiling point 147.8 ° C), methyl n-amyl ketone (boiling point 150. 6 ° C), cyclohexanone (boiling point 156 ° C), methylcyclohexanone (boiling point 169.0 ⁇ 170.
  • diisoptyl ketone (boiling point 168 ° C), diacetone alcohol (boiling point 166-169.1 ° C), methylhexyl ketone (boiling point 174 ° C), fenthion (boiling point 191 ° C), Examples include acetonylaceton (boiling point: 192.2 ° C), acetophenone (boiling point: 201.7 ° C), and isophorone (boiling point: 215.2 ° C).
  • ester ether solvents having a boiling point of 135 to 225 ° C include cellosolve acetate (boiling point 135 to 160 ° C), methyl acetate solve (boiling point 144 ° C), and ethyl acetate solvate (boiling point 156 ° C).
  • Examples thereof include methoxybutyl acetate (boiling point 166 to 176 ° C), butyl acetate mouthsolve (boiling point 188 to 195 ° C), carbitol acetate (boiling point 204 to 225 ° C), and the like.
  • Examples of high-boiling amide solvents include N-methyl-2-pyrrolidone (boiling point 204 ° C), N, N dimethylacetamide (boiling point 165 ° C), N, N-dimethylformamide (boiling point 153 ° C). ) And the like.
  • the high-boiling polar organic solvent these same or different solvents may be mixed and used.
  • the organic solvent (D) needs to be at least 5 ° C higher than the boiling point of the organic solvent (C).
  • this boiling point difference is based on the following criteria when using two or more types of solvents (three or more types as a system).
  • the solvent having the largest use amount (mass) is used as the reference solvent, and when the use amount is the same, the solvent having the highest boiling point is used as the reference solvent.
  • the solvent with the highest usage (mass) is the reference solvent, and if the usage is the same, the solvent with the highest boiling point is the reference solvent. Therefore, in some cases, the boiling point difference between the organic solvent (D) and the reference solvent as a part of the organic solvent (C) is less than 5 ° C or more.
  • organic solvent with a higher boiling point is present, or if the difference in boiling point between the organic solvent (C) and the reference solvent of the organic solvent (C) as a part of the organic solvent (D) is less than or lower than 5 ° C Some organic solvents may be present.
  • the difference in boiling point is 5 ° C or more, it may be selected experimentally depending on the type and combination of solvents, but is preferably 10 ° C or more, and more preferably 30 ° C or more.
  • the upper limit may be determined in consideration of the ease of preparation of the coating composition and the stability of the composition.
  • a low-boiling polar organic solvent (D2) having a boiling point of less than 115 ° C may be further present as the polar organic solvent.
  • This low-boiling polar organic solvent (D2) is usually blended in order to uniformly disperse the hydrophilic particles when preparing the coating composition. Since (D1) exists, the dispersion uniformity of the hydrophilic particles can be maintained.
  • Examples of such low-boiling polar organic solvents (D2) include methanol (boiling point 65 ° C), ethanol (boiling point 78 ° C), isopropanol (boiling point 82.4 ° C), isopropyl alcohol (boiling point 82.3).
  • the organic solvent for polymer (C) also has a difference in boiling point from other organic solvents (D) as long as it is in a small amount (less than the main organic solvent for polymer (C)).
  • an organic solvent (C) having a boiling point lower than 5 ° C or higher than that of the other organic solvent (D) may be blended.
  • the specific combination of the organic solvent for polymer (C) and the other organic solvent (D) is a combination of hydrophilic particles. In addition, it is determined by the type of hydrophobic polymer for paint and various additives such as pigments.
  • the organic solvent for polymer (C) and the other organic solvent (D) in the antifouling coating composition of the present invention Preferable combination of the organic solvent for polymer (C) and the other organic solvent (D) in the antifouling coating composition of the present invention!
  • the nonpolar organic solvent (C1) and the high boiling point are used.
  • Examples include polar organic solvents (D 1). Specific examples of these combinations are illustrated, but the present invention is not limited to these examples.
  • the inside of Katsuko is the boiling point (° C).
  • hydrophilic fine particles used in the present invention silica fine particles, titanium oxide fine particles, apatite fine particles, photocatalytic functional apatite fine particles, metal (copper, etc.) fine particles, etc. are preferable, and two or more kinds are used in combination. May be.
  • colloidal silica for example, colloidal silica, fumed silica and the like are suitable.
  • colloidal silica examples include methanol dispersions such as MA-ST (number average particle diameter 10-15 nm) and MA-ST-MS (number average particle diameter 17-23 nm) manufactured by Nissan Chemical Co., Ltd .; Isopropanol dispersions such as IPA—ST (number average particle size 10-15 nm), IPA—ST—MS (17-23 nm), IPA ST— L (40-50 nm); MEK—ST (number average particle size 10-15 nm) ), MEK—ST—MS (number average particle size 17-23 nm) and other methyl ethyl ketone dispersions; MIBK—ST (number average particle size 10-15 nm) and other methyl isobutyl ketone dispersions, PM A—ST (number average) Examples thereof include propylene glycol monomethyl ether acetate
  • the titanium oxide fine particles may be inert acid titanium oxide! / Titanium oxide having a photocatalytic function may be used.
  • the former among those normally used as pigment fillers, fine particles can be used.
  • the photocatalytic functional acid oxide titanium fine particles include ST-0 manufactured by Ishihara Sangyo Co., Ltd.
  • Titanium oxide coating solution for photocatalysts TKS-201, TKS-202, TKC-301, TKC-302, TKC-303, TKC-304, TKC-305, TKC-351, TKC-352, acid catalyst for photocatalyst Titansol TKS-201, TKS-202, TKS-203, TKS-251, PTA, TO, and soot made by Azitex Co., Ltd. can be mentioned. However, it is possible to use materials other than these titanium oxides.
  • titanium oxide may be surface-treated with apatite.
  • apatite By treating with apatite, the effect of adsorbing bacteria and viruses is enhanced, and the sterilizing ability of the obtained coating film is improved.
  • titanium oxide particles having photocatalytic ability it can be used in combination with the hydrophilic particles in the present invention only for the purpose of photocatalytic ability and bactericidal ability. (For example, exceeding 200 nm) or hydrophobic particles.
  • apatite fine particles may be represented by the formula:
  • A is a metal atom such as Ca, Co, Ni, Cu, Al, La, Cr, Fe, Mg, B is P or S, and X is a hydroxyl group or a halogen atom
  • A is a metal atom such as Ca, Co, Ni, Cu, Al, La, Cr, Fe, Mg
  • B is P or S
  • X is a hydroxyl group or a halogen atom
  • This apatite can also be produced with a particle size of about 10 nm and has good uniform dispersibility like the silica fine particles.
  • the apatite having a photocatalytic function includes, for example, at least a part of a metal atom A (for example, Ca) in a composite metal oxide (for example, calcium hydroxyapatite) represented by the above formula as a T source. Substituted with atoms capable of imparting photocatalytic activity, such as children, and disclosed in detail in JP 2000-327315, JP 2003-175338, JP 2003-334883, and the like! The
  • this photocatalytic functional apatite deteriorates the base polymer. It is also excellent in durability as a coating film that is less likely to be applied. Furthermore, particles with a particle size of about lOnm can be produced, and the uniform dispersibility is good as with the silica fine particles.
  • the photocatalytic functional apatite particles can be used in combination with the hydrophilic particles in the present invention only for the purpose of the photocatalytic ability and bactericidal ability, in which case a relatively large particle size (for example, 200 nm) Or a hydrophobic particle.
  • the ratio of the hydrophilic particles (A) Z hydrophobic polymer (B) must be in the range of 1Z99 to 50Z50 (mass% ratio), preferably 1 to 99 to 45 to 55 (mass% ratio).
  • the hydrophilic particles specifically improve the antifouling effect within this specific content range.
  • the preferred content range may be appropriately selected depending on the type of hydrophilic particles ( ⁇ ), the type and amount of organic solvent (D), the type of coating polymer ( ⁇ ), the additive used, etc.
  • the effect may be obtained even if it is 5 to 95 (mass% ratio) or less, and it should be selected within the range of 1/99 (mass% ratio) to 30 to 70 (mass% ratio). desirable.
  • the hydrophobic polymer for coating ( ⁇ ) that forms the matrix of the coating film depends on the hydrophilic particles in consideration of the dispersibility of the hydrophilic particles ( ⁇ ) and the difference in contact angle with water. If appropriately selected, those having a contact angle with water of 60 degrees or more can be suitably employed. In addition, whether it is oleaginous or elastomeric, it is preferred that the cross-linkable polymer also has a point that can improve the mechanical properties of the coating film, even if it is V or misaligned!
  • the hydrophobic polymer ( ⁇ ) for paints is preferably a non-fluorine type hydrophobic polymer in terms of cost, workability (baking conditions), handling properties when preparing paints, etc. It may be a polymer of ⁇ .
  • hydrophobic resin for paint examples include acrylic resin, acrylic silicon resin, fluorine resin, silicone resin, urethane resin, polyester, and polyolefin. Specifically, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, stearyl (meth) acrylate Esters of (meth) acrylic acid such as rate; styrene, butyltoluene, etc.
  • Aromatic butyl monomers such as ethylene, propylene and butylene; fluorine-containing monomers such as tetrafluoroethylene, trifluoroethylene, bi-lidene fluoride, trichlorotrifluoroethylene and perfluorooctylethyl (meth) acrylate
  • a hydrophobic monomer such as butyl chloride alone, the hydrophobic monomers, or other ethylenically unsaturated monomers copolymerizable therewith.
  • Preferred examples of such a copolymer are listed below.
  • Suitable hydrophobic resins include acrylic resin, acrylic silicon resin, and urethane resin, which are advantageous in terms of cost, availability, and versatility.
  • the acrylic resin is preferably a crosslinkable acrylic resin having a functional group, and the hydrophobicity of the resin can be controlled by controlling the hydrophobicity of the substituent of the ester moiety.
  • acrylic silicone resin room temperature curable acrylic silicone resin is particularly preferable.
  • Commercially available products include, for example, Ataridec A-9540, a low glass transition point acrylic silicon resin manufactured by Dainippon Ink and Chemicals, and Ataridec BZ 1161, a high glass transition point acrylic silicon resin. Can be illustrated.
  • the fluorine resin can be selected from conventionally known fluorine resins, but is advantageous in terms of weather resistance, paint properties, solvent solubility, and the like. Therefore, tetrafluoroethylene (TFE), black mouth A copolymer mainly composed of trifluoroethylene (CTFE) and hexafluoropropylene (HFP) is preferable. These fluorinated resins are preferably crosslinkable having functional groups. Examples of commercially available products include the Zaffle series manufactured by Daikin Industries, Ltd.
  • a functional group-containing acrylic silicon-based resin is particularly preferable for silica fine particles, acid titanium fine particles, photocatalytic functional apatite fine particles, and metal fine particles.
  • the curing agent for example, when the curable functional group of the crosslinkable polymer is a hydroxyl group, a carboxyl group, an epoxy group, an amino group, a methylol group, an amide group, etc., dimethyldimethoxysilane, methyltrimethoxysilane, tetra Methoxysilane, Jetyljetoxysilane, Ethyl Preferable examples include silane compounds such as triethoxysilane, tetraethoxysilane, and their condensates. Examples of commercially available products include Ataridec A-9585 and Ataridec FZ-523 manufactured by Dainippon Ink and Chemicals, Inc.
  • Various dispersants may be used in order to improve the dispersibility of solids such as hydrophilic particles.
  • a dispersant that does not exist on the surface of the hydrophilic particles after the coating film is formed is used.
  • a low molecular weight dispersant that volatilizes when the coating film is dried is preferable.
  • a dispersant that volatilizes or decomposes during baking can be used even if it is a high molecular weight dispersant.
  • additives may be blended within a range not impairing the effects of the present invention.
  • additives include pigments, dyes, fillers, antioxidants, leveling agents, reinforcing fibers, ultraviolet absorbers, photocatalysts, and light stabilizers.
  • the blending amount of the other organic solvent (D) is an amount that can uniformly disperse the hydrophilic particles at the above-mentioned specific concentration, and can maintain the dispersed state during drying and curing of the coating film.
  • the particle (A), the hydrophobic polymer for paint (B), and the organic solvent (C) are appropriately selected depending on the type and amount. However, if the amount is too small, the dispersion stability of the hydrophilic particles may be reduced during drying, and if the amount is too large, it may take too long to dry.
  • 50 parts by mass or more, more preferably 100 parts by mass or more is preferable with respect to 100 parts by mass of the hydrophilic particles, 10,000 parts by mass or less, and further preferably 2,000 parts by mass or less.
  • the amount of the organic solvent (C) should be an amount that can uniformly dissolve or disperse the hydrophobic polymer for coating! However, if it is too small, the film thickness of the hydrophobic polymer is too early. Thus, the organic solvent (D) may be volatilized, and if it is too much, the hydrophilic particles may not be able to form a coating film while maintaining uniform dispersibility.
  • 100 parts by mass or more, more preferably 200 parts by mass or more is preferable with respect to 100 parts by mass of the hydrophobic polymer for coatings, and 10,000 parts by mass or less, and more preferably 2,000 parts by mass or less are preferable.
  • the concentration of the hydrophobic polymer for paint (B) in the composition depends on the type and amount of hydrophilic particles (A), the type of hydrophobic polymer for paint (B), the type of organic solvent (C), It is appropriately selected according to the amount. Usually, 2% by mass or more, further 5% by mass or more is preferable, 50% by mass or less, and further 20% by mass or less is preferable.
  • the composition of the present invention is prepared by mixing an organic solvent (C) solution (or dispersion) of a hydrophobic polymer for paint with an organic solvent (D) dispersion (or solution) of hydrophilic particles. This can be done by
  • the coating method is not particularly limited as long as it is a method capable of forming a uniform coating film, such as a brush coating method, a spray method, a datebing method, and a mouth coat method.
  • a drying treatment including natural drying, a curing (crosslinking) treatment, a baking treatment, and the like can be appropriately performed depending on the type of the hydrophobic polymer for coating.
  • the film thickness of the coating film is not particularly limited, but it is 200 nm or more, further 500 nm or more, particularly 5 ⁇ m or more in that a coating film having coating film strength and appropriate antifouling property can be formed. LV preferred.
  • the upper limit is not particularly limited as long as the coating does not crack.
  • the organic solvent (C) and the organic solvent (D) are volatilized and dispersed in the coating composition while maintaining a uniform dispersion state of the hydrophilic particles during drying.
  • the dispersion state is substantially maintained in the dried film.
  • the hydrophobic polymer (B) is used as the coating polymer. It is also possible to use a hydrophilic polymer as the coating polymer. In this case, the hydrophilic polymer is used instead. A hydrophobic material may be used. However, this combination is inferior to the combination of the present invention in terms of price, and this is a subject for further study.
  • conductive materials such as conductive polymers, conductive metal fillers, carbon nanotubes, carbon nanohorns, etc., and dispersing them on the surface of the coating improves the antistatic effect of the coating and improves electrostatic adhesion. It is possible to further prevent the adhesion of the sexual substance. [0104] In order to obtain such an excellent antistatic effect, it is desirable that the surface resistance value be 10 12 ⁇ or less.
  • Adopting antibacterial and antifungal functions such as Ag, Zn and Cu as hydrophilic particles in addition to preventing adhesion to the coating surface.
  • the impact resistance of the coating film surface can be improved.
  • photodegradability can be imparted by using particles having photocatalytic activity, such as anatase-type acid-titanium.
  • the particles having a photocatalytic function may have a relatively large particle diameter or may be hydrophobic.
  • the antifouling coating composition of the present invention can be applied to, for example, the following articles.
  • anti-thrombotic materials anti-protein adhesion materials
  • fat and lipid adhesion prevention materials are also useful as daily necessities.
  • Heat exchanger fins defrost countermeasures
  • roofing materials coated on tiles, etc.
  • antennas power transmission lines
  • power transmission lines prevention of cutting and destruction due to snow, etc.
  • ship exterior prevention of icing
  • ice trays ice machines
  • refrigerators Freezer (room, car)
  • glass variable vehicles, buildings
  • outdoor telecommunications equipment variable antennas such as parabolic antennas, communication towers, communication cables, wires, power transmission towers, etc.
  • transportation vehicles ships and Decks such as trains, steps for getting on and off various vehicles, pantographs, exterior projecting vehicles such as Tori Lines, aircraft wings, exteriors of various vehicles), building-related items (exteriors such as roof tiles and tiles), Roads, sidewalks (easy snow removal and deicing are easy to freeze), shoe soles, tires (hard to freeze), salt damage prevention paint, insulators (flashover prevention), etc.
  • Indoor building materials (ceiling materials, wall materials, wallpaper, etc.), blinds, curtains, flooring, carpets, transparent materials (light covers, glass, show windows, instrument covers, glasses, goggles, etc.), mirrors (for vehicles) Mirrors, home use, wash mirrors, etc.), heat exchangers, air conditioners (fans, exteriors, etc.), air conditioner ducts, air purifiers, humidification hoses (indoors, prevention of allergens such as bacteria) ), Outlets, exhaust outlets, surrounding parts, wigs, artificial hair, kitchen, range hoods, clothes (no odor transfer), cosmetics (no odor transfer), etc.
  • Dust (approximately 0.1 to 50 m), salt crystals along the coast (approximately 0.1 to LO / z m), droplets (approximately 10 to 50 / ⁇ ⁇ ), automobile exhaust, etc.
  • Outdoor building materials outer walls of buildings, exteriors of vehicles, ships, aircraft, etc.
  • road-related materials guide rails, signs, signals, tunnel walls, lighting equipment, sign covers, soundproof walls, elevated bridges, bridges, etc.
  • Transparent parts outdoor lighting cover, glass, signboard cover, show window, warm room, solar battery cover, solar water heater cover, instrument cover, glasses, goggles, etc.
  • mirror vehicle mirror, road mirror, etc.
  • Heat exchangers air conditioners (fans, exteriors, etc.), air conditioner ducts, humidification hoses (prevention of allergens such as soot in the room and bacteria), outlets, exhaust outlets, their surroundings, inside the chimney , Its surroundings, wigs, artificial hair, outing clothes (no odors, etc.), cosmetics (no odors, etc.), playground equipment (amusement park or park equipment).
  • Various conductive substances such as carbon and carbides, etc., and the attached substances are impregnated with moisture to become conductive.
  • Terminal blocks for various electrical and electronic parts plugs such as magnet plugs, and discharging parts such as electrostatic precipitator ion generators.
  • Air conditioners especially indoor air conditioners and air purifiers, which are typical examples of equipment installed in such places, have surface contamination (especially oil smoke, cigarette smoke, indoor fine powder and Prevention (such as dust) has been a challenge for many years.
  • surface contamination especially oil smoke, cigarette smoke, indoor fine powder and Prevention (such as dust) has been a challenge for many years.
  • indoor air conditioners are generally prone to dirt so that the surface needs to be cleaned 2-3 times a month.
  • the antifouling coating film of the present invention is most suitable as a coating film on the exterior and duct of such an air conditioner, in particular, on the exterior and inside of the air conditioner made of resin.
  • the air conditioner and air purifier on the surface can suppress discoloration and greatly reduce the number of cleanings.
  • Hydrophobic polymer for coatings Dainippon Ink & Chemicals, Inc. High glass transition temperature room temperature curing type tertiary amino group-containing acrylic silicone resin (Tg90 ° C) in toluene Z isobutanol solution: solid content 44% by weight.
  • Silicone hardener (trade name Ataridec FZ—523, manufactured by Dainippon Ink and Chemicals, Inc.)
  • Hydrophilic particles colloidal sill force (.. Nissan Chemical Co., Ltd. IPA-ST number average particle diameter 10 ⁇ 15nm silica 30-31 mass 0/0 of isopropanol dispersion)
  • Example 1 TEM photograph of the cross section of the coating film of Sample 1. Magnification 160,000), the surface roughness a is in the range of 5 to 20 nm.
  • Example 2 TEM photograph of the cross section of the coating film of Sample 2. Magnification 160,000), the surface roughness a is in the range of 5 to 20 nm.
  • Example 3 TEM photograph of the cross section of the coating film of Sample 3. Magnification 160,000), the surface roughness a is about 30 nm.
  • a test apparatus described later was prepared and used.
  • Commercial cigarettes generated by a smoke generator (mild seven manufactured by Nippon Tobacco Co., Ltd.) Put 10 smokes into the water tank for evaluation, and stir well with the fan provided in the water tank. Then, when the smoke inside the water tank becomes homogeneous, stop the fan, put the sample fixed on the test material jig into the water tank, and measure the dirt after 10 hours.
  • This test apparatus is composed of a smoke generator 1, an evaluation water tank 2, and a sample jig 3.
  • the smoke generator 1 includes a pump 7 for sending air for burning tobacco, a container 6 for burning tobacco, and a dehumidifying unit 4 for dehumidifying the smoke of the tobacco 5, and generates dry smoke.
  • the test water tank 2 is made of glass having a width of 600 X a length of 300 X a height of 380 mm, and is provided with a fan 8 for smoke stirring on the side surface.
  • the lid on the top of the tank 2 has an inlet for smoke 10 from the smoke generator, an opening for taking in and out the sample 9, and a temperature and humidity meter for measuring the temperature and humidity in the tank. Is provided.
  • the sample jig 3 is configured so that the sample 9 can be taken in and out of the water tank 2 and the sample 9 can be fixed at a fixed position in the water tank 2.
  • the structure of the antifouling coating film that can exhibit an excellent antifouling effect even when using a general-purpose hydrophobic polymer for paints, which is a small amount of hydrophilic particles and inexpensive compared to conventional ones. Provide It can be done.

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Abstract

La présente invention concerne une structure d'un film de revêtement résistant aux taches qui peut présenter un excellent effet anti-tache même lorsque le film de revêtement est produit à l'aide d'une quantité moins importante de particule hydrophile que dans un film conventionnel et de polymère de revêtement hydrophobe peu coûteux à usages multiples. Une structure d'un film de revêtement résistant aux taches comprend (A) 10 à 50 parties en masse d'une particule hydrophile dispersée dans (B) 100 parties en masse d'un polymère hydrophobe, la particule hydrophile (A) présentant un diamètre de particule moyen en nombre de 50 nm ou moins et la surface libre du film de revêtement présentant une rugosité (a) de 50 nm ou moins telle que mesurée avec une longueur de référence de 500 nm.
PCT/JP2006/310217 2005-05-25 2006-05-23 Structure de film de revetement resistant aux taches WO2006126521A1 (fr)

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KR20080012393A (ko) * 2008-01-17 2008-02-11 김재호 고 내마모성 및 고 투명성의 수용성 광경화형 대전방지조성물 및 이를 코팅한 전도성 타일 바닥재
JP4698721B2 (ja) * 2008-10-17 2011-06-08 三菱電機株式会社 空気調和機及びコーティング組成物
SI2218740T1 (sl) * 2009-02-13 2014-03-31 Bayer Materialscience Llc ÄŚistilni poliuretanski premazi na vodni osnovi
JP2011208937A (ja) * 2011-06-30 2011-10-20 Mitsubishi Electric Corp 空気調和機及びコーティング組成物
JP2017150736A (ja) * 2016-02-24 2017-08-31 株式会社Uacj フィン材及び熱交換器
JP6399467B1 (ja) * 2017-11-21 2018-10-03 パナソニックＩｐマネジメント株式会社 自動販売機

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